Sulfur tolerant anode for solid oxide fuel cell

ABSTRACT

A solid oxide fuel cell (SOFC) ( 100 ) for use in generating electricity while tolerating sulfur content in a fuel input stream. The solid oxide fuel cell ( 100 ) includes an electrolyte ( 106 ), a cathode ( 102 ), and a sulfur tolerant anode ( 104 ). The cathode ( 102 ) is disposed on a first side of the electrolyte ( 106 ). The sulfur tolerant anode ( 104 ) is disposed on a second side of the electrolyte ( 106 ) opposite the cathode ( 102 ). The sulfur tolerant anode ( 104 ) includes a composition of nickel, copper, and ceria to exhibit a substantially stable operating voltage at a constant current density in the presence of the sulfur content within the fuel input stream. The solid oxide fuel cell ( 100 ) is useful within a SOFC stack to generate electricity from reformate which includes synthesis gas (syngas) and sulfur content. The solid oxide fuel cell ( 100 ) is also useful within a SOFC stack to generate electricity from unreformed hydrocarbon fuel.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims priority to U.S. patentapplication Ser. No. 12/240,725, filed on Sep. 29, 2008 (the '725Application). The '725 Application claims the benefit of U.S.Provisional Patent Application No. 60/975,761, filed on Sep. 27, 2007,entitled “Sulfur Tolerant Anode.” These applications are expresslyincorporated herein by reference.

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The U.S. Government has certain rights in this invention as provided forby the terms of Small Business Innovation Research (SBIR) Contract No.FA8650-07-M-2704 awarded by the U.S. Air Force.

BACKGROUND

Embodiments of this invention relate generally to the field of solidoxide fuel cells and, more specifically, to anode structures for solidoxide fuel cells.

A solid oxide fuel cell (SOFC) electrochemically converts fuel intoelectricity. The solid oxide fuel cell has a solid oxide, or ceramic,electrolyte between a cathode and an anode. A conventional solid oxidefuel cell utilizes an yttria-stabilized zirconia (YSZ) electrolytebetween the cathode and the anode. In general, the cathode reducesoxygen from the air into oxygen ions and passes the oxygen ions throughthe electrolyte to the anode. A conventional cathode material islanthanum strontium manganite (LSM), or a similar material. The anodeuses the oxygen ions to oxidize the fuel, which results in freeelectrons at the anode. The anode is typically a ceramic/metallic(cermet) material that includes YSZ as the ceramic and nickel (Ni) asthe metal. By connecting an electrical load between the anode and thecathode (outside of the fuel cell), the electrons can return to thecathode, and the electrical generation cycle can repeat.

FIG. 1 depicts a schematic block diagram of a conventional SOFC system10. The conventional SOFC system 10 includes a reformer 12, a sulfurtrap 14, and a conventional solid oxide fuel cell 16. Sulfur can rapidlypoison and deactivate the Ni-YSZ cermet anode of the solid oxide fuelcell 16. Since many fuels contain total sulfur levels that far exceedthe levels that can damage the typical anode of the solid oxide fuelcell 16, the reformer 12 and the sulfur trap 14 are used to removesulfur content from the fuel. Typical fuels which may be reformed by thereformer 12 include military fuels such as JP-8, JP-5, and NATO F-76.While military fuel sources are energy dense, these fuels are extremelycomplex in composition and contain a number of impurities and additivesthat present challenges for compact electrochemical power generation. JPfuels can contain as much as 3,000-4,000 ppm by weight sulfur, whileNavy fuels (NATO F-76, etc.) can include as much as 10,000 ppm byweight.

The reformer 12 implements a reformation process to break downhydrocarbons (C_(x)H_(y)) from the fuel into reformate which includessynthesis gas (syngas) and hydrogen sulfide (H₂ 5). The syngas includeshydrogen (H₂) and carbon monoxide (CO), and also may include othercomponents such as carbon dioxide (CO₂) and steam (H₂O). Althoughreformation by the reformer 12 reduces the sulfur content, typicalsulfur levels for reformate from JP fuels is about 500-600 ppmv from anendothermic steam reformer and 300-400 ppmv from a partial oxidation(POx) reformer.

Hydrogen sulfide (H₂S) content in the reformate of 2 ppmv (at 1000° C.)is known to poison the anode of a conventional solid oxide fuel cell 16.Additionally, sulfur poisoning increases the polarization resistance andover-voltage of the anode at as low as 0.5 ppmv (at 900° C.). Thisconcentration of H₂S is close to the equilibrium values measured at thattemperature for the chemisorption of H₂S to achieve full coverage onnickel steam-reforming catalysts. Because of this coverage, conventionalNi-YSZ cermet anodes are not sulfur tolerant.

Since the sulfur content of the reformate (i.e., syngas and sulfur) fromthe reformer 12 is significant enough to poison the anode, the reformateis directed through the sulfur trap 14 to remove the remaining sulfurcontent, leaving only the syngas. Many of the sulfur compounds presentin these fuel streams are mildly reactive and, therefore, are relativelyeasy to remove. However, there are also considerable quantities of morecomplex sulfur compounds, including substituted thiophenes, which can beparticularly difficult to remove via conventional liquid phaseadsorption processes. In addition, even with the best possible liquidphase sulfur removal technology, the conventional solid oxide fuel cellis not capable of accommodating sulfur in the fuel stream due tointermittent malfunctions of the sulfur trap 14, or another sulfurremoval system. In other words, occasional sulfur slip is anticipated.Additionally, the adsorption of liquid phase sulfur removal materialsutilizes relatively large amounts of material, which increases the sizeand resources of the conventional SOFC system 10.

In contrast to the conventional Ni-YSZ cermet anodes, other conventionalSOFC devices use a doped ceria (cerium oxide (CeO₂)) anode or acopper-ceria (Cu—CeO₂) anode. While ceria provides sulfur tolerance andsome avoidance of coking if there is hydrocarbon slip, ceria is a mixedconductor in a fuel atmosphere and has low electronic conductivity.Thus, ceria alone does not provide a low polarization loss for a highperformance anode. Infiltration of cerium nitrate (Ce(NO₃)₃) into aconventional Ni-YSZ cermet anode may show some level of tolerance to thepresence of H₂S.

SUMMARY

Embodiments of an apparatus are described. In one embodiment, theapparatus is a solid oxide fuel cell (SOFC). The solid oxide fuel cellmay be implemented to generate electricity while tolerating sulfurcontent in a fuel input stream. The solid oxide fuel cell includes anelectrolyte, a cathode, and a sulfur tolerant anode. The cathode isdisposed on a first side of the electrolyte. The sulfur tolerant anodeis disposed on a second side of the electrolyte opposite the cathode.The sulfur tolerant anode includes a composition of nickel, copper, andceria to exhibit a substantially stable operating voltage at a constantcurrent density in the presence of the sulfur content within the fuelinput stream. Other embodiments of the solid oxide fuel cell are alsodescribed.

The solid oxide fuel cell is useful within a SOFC stack, which includesa plurality of solid oxide fuel cells coupled together, for example, ina serial configuration. Embodiments of the SOFC stack are useful togenerate electricity from reformate which includes synthesis gas(syngas) and sulfur content. Embodiments of the SOFC stack are alsouseful to generate electricity from unreformed hydrocarbon fuel. Otherembodiments of a SOFC system which uses a SOFC stack with sulfurtolerant anodes are also described.

Embodiments of a method are also described. In one embodiment, themethod is a method of making a solid oxide fuel cell. The methodincludes disposing a cathode on a first side of an electrolyte. Themethod also includes disposing a sulfur tolerant anode on a second sideof the electrolyte. The sulfur tolerant anode operates at asubstantially stable operating voltage at a constant current density inthe presence of a fuel with a measurable sulfur content. In someembodiments, nitrates or oxides may be mixed and calcined using aPechini or glycine nitrate process and the resulting anode disposed onthe electrolyte. In some embodiments, a mixture of components may bedisposed on the electrolyte using a solid state process. In someembodiments, the mixture of components may be a mixture or nitrates orfine particles (e.g., nanoparticles) which are infiltrated into a porousmaterial, such as the electrolyte or an inert material disposed on theelectrolyte.

Some embodiments may combine two or more of the various structuresand/or functions described herein. Other aspects and advantages ofembodiments of the present invention will become apparent from thefollowing detailed description, taken in conjunction with theaccompanying drawings, illustrated by way of example of the principlesof the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic block diagram of a conventional solid oxidefuel cell (SOFC) system.

FIG. 2 depicts a schematic block diagram of one embodiment of a sulfurtolerant solid oxide fuel cell.

FIG. 3 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell of FIG. 2, including a catalystdisposed on the anode.

FIG. 4 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell of FIG. 2 with the anodeinfiltrated into a portion of the electrolyte.

FIG. 5 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell of FIG. 4 with a graded ceriaanode.

FIG. 6 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell of FIG. 4 with a graded copperanode.

FIG. 7 depicts a schematic block diagram of one embodiment of a SOFCsystem which includes the sulfur tolerant solid oxide fuel cell of FIG.2.

FIG. 8 depicts a schematic block diagram of another embodiment of a SOFCsystem which includes the sulfur tolerant solid oxide fuel cell of FIG.2.

Throughout the description, similar reference numbers may be used toidentify similar elements.

DETAILED DESCRIPTION

It will be readily understood that the components of the embodiments asgenerally described herein and illustrated in the appended Figures couldbe arranged and designed in a wide variety of different configurations.Thus, the following more detailed description of various embodiments, asrepresented in the Figures, is not intended to limit the scope of thepresent disclosure, but is merely representative of various embodiments.While the various aspects of the embodiments are presented in drawings,the drawings are not necessarily drawn to scale unless specificallyindicated.

The present invention may be embodied in other specific forms withoutdeparting from its spirit or essential characteristics. The describedembodiments are to be considered in all respects only as illustrativeand not restrictive. The scope of the invention is, therefore, indicatedby the appended claims rather than by this detailed description. Allchanges which come within the meaning and range of equivalency of theclaims are to be embraced within their scope.

Reference throughout this specification to features, advantages, orsimilar language does not imply that all of the features and advantagesthat may be realized with the present invention should be or are in anysingle embodiment of the invention. Rather, language referring to thefeatures and advantages is understood to mean that a specific feature,advantage, or characteristic described in connection with an embodimentis included in at least one embodiment of the present invention. Thus,discussion of the features and advantages, and similar language,throughout this specification may, but do not necessarily, refer to thesame embodiment.

Furthermore, the described features, advantages, and characteristics ofthe invention may be combined in any suitable manner in one or moreembodiments. One skilled in the relevant art will recognize, in light ofthe description herein, that the invention can be practiced without oneor more of the specific features or advantages of a particularembodiment. In other instances, additional features and advantages maybe recognized in certain embodiments that may not be present in allembodiments of the invention.

Reference throughout this specification to “one embodiment,” “anembodiment,” or similar language means that a particular feature,structure, or characteristic described in connection with the indicatedembodiment is included in at least one embodiment of the presentinvention. Thus, the phrases “in one embodiment,” “in an embodiment,”and similar language throughout this specification may, but do notnecessarily, all refer to the same embodiment.

In the following description, specific details of various embodimentsare provided. However, some embodiments may be practiced without atleast some of these specific details. In other instances, certainmethods, procedures, components, and circuits are not described indetail for the sake of brevity and clarity, but are neverthelessunderstood from the context of the description herein.

In general, the described embodiments are directed to a sulfur tolerantanode for a solid oxide fuel cell (SOFC). Since typical hydrocarbonfuels have sulfur content, and sulfur can irreparably damage the anodeof a conventional solid oxide fuel cell, embodiments described hereinrelate to a solid oxide fuel cell with an anode that is tolerant ofsulfur. The sulfur tolerance of the anode may be manifested by theability of the solid oxide fuel cell to generate electricity at asubstantially stable operating voltage at a constant current density,even though the operating voltage may be relatively lower when sulfur ispresent in the input field stream.

Various improvements can be made over an anode of a conventional solidoxide fuel cell in order to improve the sulfur tolerance of the solidoxide fuel cell. In one embodiment, some or all of the YSZ, in aconventional Ni-YSZ, cermet anode can be replaced with doped ceria. Thedoped ceria contributes to sulfur tolerance of the anode. The dopedceria also contributes to coke suppression at the anode.

In another embodiment, some of the nickel in a conventional Ni-YSZcermet anode can be replaced with an electrochemically inert oxidematerial. Some examples of electrochemically inert oxide materialsinclude thorium oxide (ThO₂), zirconium oxide (ZrO₂), magnesium oxide(MgO), a titanium oxide (TiO₂), potassium oxide (K₂O), and a. tungstenoxide (WO₂), although other embodiments may use other electrochemicallyinert oxide materials. The addition of the electrochemically inert oxidematerial contributes to sulfur tolerance and coke suppression of theanode.

In another embodiment, copper is added to the anode structure. Thecopper contributes to oxidation of some hydrocarbons. Thus, the copperwithin the anode facilitates direct oxidation of certain hydrocarbonfuels. When combined with the sulfur tolerance properties achieved bythe addition of ceria and the electrochemically inert oxide material(e.g., MgO), the direct oxidation by the copper allows a hydrocarbonfuel source with sulfur content to be processed by the solid oxide fuelcell without significant degradation of the performance of the solidoxide fuel cell.

By implementing a sulfur tolerant anode in a solid oxide fuel cell, thesolid oxide fuel cell may be used in a system with a reformer and asulfur trap, even if the sulfur trap malfunctions and allows sulfur toreach the solid oxide fuel cell. Also, the solid oxide fuel cell with asulfur tolerant anode may be used in a system which omits the sulfurtrap, so that the solid oxide fuel cell processes reformate whichincludes syngas and sulfur content. Additionally, the solid oxide fuelcell with the sulfur tolerant anode may be used in a system which omitsboth the reformer and the sulfur trap, so that the solid oxide fuel cellwith the sulfur tolerant anode processes hydrocarbon fuel using directoxidation. The omission of the sulfur trap and/or the reformer from aSOFC power generation system allows embodiments of the SOFC powergeneration system to be made lighter, simpler, and more reliable.

FIG. 2 depicts a schematic block diagram of one embodiment of a sulfurtolerant solid oxide fuel cell 100. The illustrated sulfur tolerantsolid oxide fuel cell 100 includes a cathode 102, a sulfur tolerantanode 104, and an electrolyte 106. In general, the cathode 102 extractsoxygen (O₂) from an input oxidant (e.g., ambient air) and reduces theoxygen into oxygen ions. The remaining gases are exhausted from thesolid oxide fuel cell 100. The electrolyte 106 diffuses the oxygen ionsfrom the cathode 102 to the anode 104. The anode 104 uses the oxygenions to oxidize hydrogen (H₂) from the input fuel (i.e., combine thehydrogen and the oxygen ions). The oxidation of the hydrogen forms water(H₂O) and free electrons (e⁻). The water exits the anode 104 with anyexcess fuel and sulfur. The free electrons can travel through a circuit(shown dashed with a load 108) between the anode 104 and the cathode102. When combined with other solid oxide fuel cells 100 within a SOFCstack, the power generation capabilities of all of the solid oxide fuelcells 100 can be combined to output more power.

The anode 104 is sulfur tolerant and, in some embodiments, receives fuelwith sulfur content. The fuel may be reformate which includes syngas andsulfur. Alternatively the fuel may be a hydrocarbon fuel which includessulfur containing compounds. Although embodiments of the solid oxidefuel cell are described herein as being sulfur tolerant and capable ofprocessing fuel in the presence of sulfur, without significantdegradation, embodiments of the solid oxide fuel cell are also capableof processing fuel in the absence of sulfur.

One example of a sulfur tolerant anode 104 is an anode formed withnickel, copper, magnesium oxide, and ceria (e.g., Ni—Cu—MgO—ceria). Thenickel in the anode 104 contributes to oxidation of hydrogen and carbonmonoxide. The magnesium oxide decreases the amount of nickel andincreases the sulfur tolerance of the anode 104. The magnesium oxidealso suppresses coke formation at the anode 104. Although magnesiumoxide is specifically referenced in this example, other embodiments mayuse other types of electrochemically inert oxide materials. The ceria inthe anode 104 also increases sulfur tolerance of the anode 104 andsuppresses coke formation at the anode 104. The copper allows directoxidation of certain hydrocarbons. The copper also maintains arelatively high conductivity of the anode 104. Thus, the combination ofnickel, copper, magnesium oxide, and ceria results in an anode structure104 which is substantially sulfur tolerant and coke resistant, whilemaintaining a relatively high conductivity. The sulfur tolerance anddirect oxidation capabilities of the anode 104 allow embodiments of thesolid oxide fuel cell 100 to directly process hydrocarbon fuels whichmight have sulfur content associated with the fuel.

The sulfur tolerant anode 104 may be made and disposed on theelectrolyte 106 using any suitable technique. In one embodiment, theanode materials are applied to a porous surface of the electrolyte 106so that the anode materials at least partially infiltrate theelectrolyte 106. An example of infiltrating the electrolyte 106 withanode materials is shown in FIG. 4 and described in more detail below.In contrast to infiltration techniques, some embodiments of the solidoxide fuel cell 100 implement the anode materials disposed substantiallyon a surface of the electrolyte 106, rather than infiltrating thestructure of the electrolyte 106.

In one embodiment, the anode materials are synthesized using a Pechini,or glycine nitrate, process. In general, the Pechini process involvesmixing nitrates of the anode materials (e.g., Ni, Cu, Co, Mg, ceria, anda dopant for the ceria) with ethylene glycol and citric acid, charringthe mixture at about 150° C., calcining the char at about 1000° C., andmilling the resulting material. The resulting anode is made into a pasteusing a binder and solvent system, and the paste is screen printed ontothe electrolyte 106 and fired. The Pechini process is described ingreater detail in U.S. Pat. No. 3,330,697, entitled “Method of preparinglead and alkaline earth titanates and niobates and coating method usingthe same to form a capacitor.”

In another embodiment, the anode materials are synthesized using a solidstate process. In one embodiment, oxides and carbonates of the anodecomponents are admixed and calcined to obtain a two phase mixture. Aresulting anode powder is made into a paste using a binder, and thepaste is screen printed onto the electrolyte 106, which is then fired.

Thus, in various embodiments, raw materials in the form of nitrates,oxides, and carbonates of copper, nickel, and one or more inert oxides,as appropriate for Pechini, glycine nitrate, solid state or any knownprocess for ceramic and cermet powder manufacture, are used as thestarting materials. When the anode material is prepared, the anodematerial contains a mixture of the oxides of nickel, copper, and theinert oxide. The oxides of nickel, copper, and the inert oxide may be inthe form of a solid solution or as separate oxide phases. When exposedto the fuel gas such as hydrogen or syngas, only the NiO and CuO in thesolid solution is reduced to a metallic phase as distinct nickel andcopper, or more commonly as an alloy of Ni and Cu, leaving an extremelyfine dispersion of the inert oxide. One example of the inert oxide isMgO, although other inert oxides are described herein. In particular,other inert oxides that have at least 1 to 20 mole percent solubility inthe (NiCu)O solid solution can also be employed. With a solid solutionof NiO, CuO, and MgO, there is a substantial region of the phase diagram(not shown) where the solid solution of the three oxides is present as(Mg, Ni, Cu)O. In all cases, only the oxides of Ni and Cu reduce to themetallic phase, leaving a fine dispersion of inert oxide in the metalgrains.

FIG. 3 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell 100 of FIG. 2, including acatalyst 110 disposed on the anode 104. The catalyst 110 alsocontributes to the sulfur tolerance of the anode 104. Additionally, thecatalyst 110 may improve other aspects of the electrochemicalperformance of the anode 104 and the solid oxide fuel cell 100. Thecatalyst material being present as very fine, high surface areaparticles on the interior porous surface of the anode structure enhancesthe adsorption and dissociation of the fuel molecules and enablesdiffusion of the adsorbed and dissociated species to the electrochemicalreaction sites. This improves the reaction kinetics and results inimproved performance. Some examples of catalyst materials includepraseodymium (Pr) and cobalt (Co), although other types of rare earthmetals may be used. In an embodiment which uses cobalt as the catalyst110, the anode structure can be described, generally, by the chemicalformula Ni—Co—Cu—MgO-ceria. In some embodiments, ceria may be used asthe catalyst 110.

The catalyst 110 is shown as a separate layer from the anode 104, but insome embodiments the catalyst 110 may be disposed within a surfaceportion of the anode 104. For example, the catalyst 110 may beinfiltrated into a portion of the anode 104. More specifically,infiltrant cations of the catalyst 110 may be introduced during anodesynthesis. In one embodiment, a liquid form of nitrates of cobalt and/orpraseodymium is impregnated into a porous anode material so that porousspaces within the anode material receive a coating of the liquidcatalyst material. Upon heating, the cobalt and praseodymium salts areconverted to cobalt and praseodymium oxides which are subsequentlyreduced to cobalt and praseodymium metals prior to operation which coatthe anode 104. In some embodiments, the resulting content of thecatalyst 110 disposed on the anode 104 is generally less than about 1%by weight, although other embodiments may result in more than 1% byweight.

FIG. 4 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell 100 of FIG. 2 with the anode 104infiltrated into a portion of the electrolyte 106. In the depicted solidoxide fuel cell 100, the anode 104 is not formed as a separate materialwhich is applied to a surface of the electrolyte 106. Rather, the anode104 is formed by infiltration of materials which are applied to a poroussurface and allowed to fill in porous spaces of the electrolyte 106.

In one embodiment, the materials are combined within a liquid mixture(e.g., a nitrate mixture) which is infiltrated into a porous portion ofthe electrolyte 106. In some embodiments, the materials are combined asfine particles (e.g., nanoparticles) which are then infiltrated into aporous portion of the electrolyte 106. The porous portion of theelectrolyte 106 may be formed of an electrolyte material such aszirconia (e.g., YSZ) or ceria. Alternatively, the mixture of anodematerials may be infiltrated into a porous inert material such asalumina (Al₂O₃) disposed on the electrolyte 106. In this embodiment, theanode materials are not infiltrated directly into the electrolyte 106,but are infiltrated into the inert material disposed on a surface of theelectrolyte 106.

FIG. 5 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell 100 of FIG. 4 with a graded ceriaanode 104. In general, the arrows within the anode 104 portion of thesolid oxide fuel cell 100 indicate an increasing concentration of ceriain the direction of the arrows and, correspondingly, a decreasingconcentration of other components such as zirconia electrolyte materialin the opposite direction. As mentioned above, the addition of ceria inthe anode 104 can enhance the sulfur tolerance of the anode 104. Theceria also suppresses coke formation at the anode 104 so that carbonparticles (e.g., from cracked hydrocarbons) do not form a film on theanode 104 and prevent the anode 104 from facilitating the oxidation offuel and generation of free electrons. However, it may be difficult todispose a ceria-based anode on the electrolyte 106.

In order to dispose a ceria-based anode on the electrolyte 106, it maybe useful to mix the ceria with at least some of the electrolytematerial. For example, the anode 104 may include a mixture of ceria andYSZ. Additionally, the mixture of ceria and YSZ may be graded within theanode 104 so that there is more electrolyte material (e.g zirconia) nearthe electrolyte 106 and more ceria near the exposed surface of the anode104. In other words, the graded ceria anode 104 has a proportionalconcentration of the ceria and the YSZ, which varies approximatelyrelative to a distance from the electrolyte 106. In this way, the higherconcentration of electrolyte material near the electrolyte 106 helps theanode 104 to be disposed on the electrolyte 106, while the higherconcentration of ceria near the exposed surface of the anode 104facilitates sulfur tolerance and coke suppression.

FIG. 6 depicts a schematic block diagram of another embodiment of thesulfur tolerant solid oxide fuel cell 100 of FIG. 4 with a graded copperanode 104. Like the graded ceria anode 104 shown in FIG. 5 and describedabove, the graded copper anode 104 of FIG. 6 has a varying concentrationof copper within the anode 104 of the solid electrolyte fuel cell 100.In the depicted embodiment, the concentration of copper within the anode104 is relatively higher at a fuel input end of the anode 104, asindicated by the arrow, and lower at a fuel output end of the anode 104.Thus, the copper concentration within the sulfur tolerant anode 104varies along a distance between a fuel input end of the sulfur tolerantanode 104 and a fuel output end of the sulfur tolerant anode 104.

While copper within the anode 104 provides direct oxidation of certainhydrocarbons, as well as suppression of coke formation, copper does notoxidize some lower hydrocarbons such as methane. Therefore, fullydistributed copper within the anode 104 (along the length of the fuelpath) may limit the type of fuel that may be processed and utilized inthe solid oxide fuel cell 100. Hence, the graded copper anode 104includes decreasing concentrations of copper along the fuel flowdirection of the anode 104. In this way, higher hydrocarbons areoxidized near the fuel entrance, or intake, and lower hydrocarbons areoxidized closer to the fuel output, or outlet. Additionally, someembodiments of the graded copper anode 104 facilitate internalreformation, in addition to direct oxidation. Thus, for these reasons,the graded copper anode 104 can facilitate higher fuel utilizationcompared with an anode that does not include copper or an anode thatonly includes evenly distributed copper.

FIG. 7 depicts a schematic block diagram of one embodiment of a SOFCsystem 120 which includes the sulfur tolerant solid oxide fuel cell 100of FIG. 2. The illustrated SOFC system 120 includes the reformer 12operably connected to the solid oxide fuel cell 100. The reformer 12 atleast partially oxidizes the fuel to produce reformate. The reformateincludes syngas and sulfur, although the sulfur concentration of thereformate may be significantly lower than the sulfur concentration ofthe unreformed fuel.

The reformate, including the syngas and sulfur, is directed from thereformer 12 to the solid oxide fuel cell 100. In contrast to theconventional SOFC system 10 illustrated in FIG. 1, the SOFC system 10 ofFIG. 7 omits the sulfur trap 14. However, the illustrated SOFC system ofFIG. 7 is also representative of a SOFC system which includes amalfunctioning, or otherwise inoperable, sulfur trap 14. In the absenceof the sulfur trap 14, or in the conditions of an inoperable sulfur trap14, the solid oxide fuel cell 100 with the sulfur tolerant anode 104 isnevertheless capable of operating to generate electricity even thoughthe reformate includes sulfur. Moreover, embodiments of the solid oxidefuel cell 100 may exhibit a substantially stable operating voltage,despite the presence of sulfur in the reformate which is used by thesolid oxide fuel cell 100.

FIG. 8 depicts a schematic block diagram of another embodiment of a SOFCsystem 120 which includes the sulfur tolerant solid oxide fuel cell 100of FIG. 2. In the illustrated SOFC system 130, both the reformer 12 andthe sulfur trap 14 are omitted. Thus, the fuel is fed directly into thesolid oxide fuel cell 100 to generate electricity. Depending on thesulfur content of the fuel, and the composition of the solid oxide fuelcell 100, the solid oxide fuel cell 100 may be capable of directlyoxidizing the fuel despite relatively high sulfur content.

It should be noted that references herein to the solid oxide fuel cell100 may also be used to refer to a stack of solid oxide fuel cells 100.The stack of solid oxide fuel cells 100 may be referred to as a SOFCstack. Thus, depictions and descriptions of an individual solid oxidefuel cell 100 are also representative of a SOFC stack. In particular,the SOFC systems 120 and 130 of FIGS. 7 and 8 may include SOFC stacksinstead of individual solid oxide fuel cells 100.

With various sulfur concentrations of different fuels, for the directoxidation the sufur concentration can be up to 15 ppm by weight and forthe syngas case the sulfur concentration could be as high as 1,000 ppmby volume. The effect of sulfur on the anode performance is stronglytemperature dependent. While sulfur concentrations as high as 200 ppmv,typical of most reformed fuel, is tolerated with only a minor loss inoperating voltage at a constant current density at 700 to 800° C.operating temperature, a much higher sulfur concentration as much as1,000 ppm can be tolerated when the cell is operated at temperatures of900 to 1000° C. Some embodiments may operate at different operatingvoltages, current densities, and/or temperatures.

At a typical constant current density operation, the anode performancewill drop only about 20 to 100 mV when sulfur containing fuel isintroduced, relative to the operating voltage of the anode when operatedwith sulfur free fuel. The exact magnitude of change is dependent on thesulfur concentration, operating current density, and temperature. Highersulfur concentration and higher current density will cause highervoltage drop. In contrast a higher operating temperature will causelower voltage drop.

More generally, the relationships among sulfur concentration, currentdensity, operating temperature, and operating voltage allows one or moreof the operating characteristics to be adjusted or optimized based onone or more of the remaining operating characteristics. Additionally,the relationship among voltage, current, and resistance can also affectthe operation of the sulfur tolerant anode. For example, the load 108could be a constant resistance load, in which case the voltage andcurrent of the solid oxide fuel cell 100 effectively go down in responseto degradation of the sulfur tolerant anode 104. Alternatively, the load108 could be a constant current load, in which case only the voltagegoes down in response to degradation of the sulfur tolerant anode 104.In another embodiment, the load 108 could be a constant voltage load, inwhich case only the current goes down in response to degradation of thesulfur tolerant anode 104. Thus, embodiments of the solid oxide fuelcell 100 can achieve a stable output power, in which the voltage andcurrent are tied to the internal cell resistance.

Although the operations of the method(s) herein are shown and describedin a particular order, the order of the operations of each method may bealtered so that certain operations may be performed in an inverse orderor so that certain operations may be performed, at least in part,concurrently with other operations. In another embodiment, instructionsor sub-operations of distinct operations may be implemented in anintermittent and/or alternating manner.

Although specific embodiments of the invention have been described andillustrated, the invention is not to be limited to the specific forms orarrangements of parts so described and illustrated. The scope of theinvention is to be defined by the claims appended hereto and theirequivalents.

What is claimed is:
 1. A method for making a solid oxide fuel cell(SOFC), the method comprising: disposing a cathode on a first side of anelectrolyte; and disposing a sulfur tolerant anode on a second side ofthe electrolyte, wherein the sulfur tolerant anode comprises a mixtureof nickel (Ni), copper (Cu), and ceria (CeO₂) to operate at asubstantially stable operating voltage at a constant current density inthe presence of a fuel with a measurable sulfur content.
 2. The methodof claim 1, wherein disposing the sulfur tolerant anode on the secondside of the electrolyte comprises: mixing nitrates of the nickel,copper, and ceria; and using a Pechini process to convert the nitratesto mixture of oxides to dispose on the electrolyte.
 3. The method ofclaim 2, further comprising mixing a nitrate of magnesium (Mg) oranother electrochemically inert ceramic oxide precursor with thenitrates of the nickel, copper, and ceria.
 4. The method of claim 2,further comprising mixing a nitrate of cobalt (Co) or a nitrate ofpraseodymium (Pr) with the nitrates of the nickel, copper, and ceria. 5.The method of claim 2, further comprising mixing the nitrate of ceriawith a. dopant.
 6. The method of claim 1, wherein disposing the sulfurtolerant anode on the second side of the electrolyte comprises: mixingnitrates of the nickel, copper, and ceria; and using a glycine nitrateprocess to convert the nitrates to mixture of oxides to dispose the onthe electrolyte.
 7. The method of claim 1, wherein disposing the sulfurtolerant anode on the second side of the electrolyte comprises: making amixture of: oxides of the nickel, copper, and ceria; anelectrochemically inert ceramic oxide; and a catalyst; and using a solidstate process to convert the oxides to mixture of oxides to dispose themixture on the electrolyte.
 8. The method of claim 1, wherein disposingthe sulfur tolerant anode on the second side of the electrolytecomprises: making a mixture of components for the sulfur tolerant anode,wherein the components comprise the nickel, copper, and ceria; and.infiltrating the mixture into a porous material.
 9. The method of claim8, wherein the mixture comprises nitrates of the nickel, copper, andceria.
 10. The method of claim 8, wherein the mixture comprises fineparticles of the nickel, copper, and ceria.
 11. The method of claim 8,wherein the porous material comprises an electrolyte material.
 12. Themethod of claim 8, wherein the porous material comprises an inertmaterial disposed on the electrolyte.